JP2013543800A - Laminate having colored layer and method for producing the same - Google Patents

Abstract

  The present invention includes at least one thermoplastic substrate and at least one colored layer, wherein the thermoplastic substrate includes polyamide, and the substrate is provided with at least one colored layer having polyurethane crosslinking. It is related with the laminated material currently used.

Description

  The present invention relates to a laminate comprising at least one thermoplastic substrate and at least one colored layer. Furthermore, this invention has described the manufacturing method of the said laminated body.

  Laminates with colored layers, in particular printed sheets, are often used for the production of decorated plastic parts with a special surface finish. In general, the colored layer is provided with a reinforcing layer, resulting in a three-layer structure in which the colored layer is disposed between the printed substrate and the reinforcing layer. This gives a very strong plastic part, the printed sheet being important for durability.

  Heretofore, however, substrates based solely on polycarbonate are known. However, the durability of polycarbonate, especially based on chemical and mechanical resistance and weather resistance, is relatively limited. Recently, for example, in the automotive field, there is a need for chemical resistance that is no longer possible with polycarbonate. For example, the plastic parts often come into contact with oils from cosmetics or foods or oil-in-water emulsions or water-in-oil emulsions that may contain relatively corrosive ingredients. Therefore, high quality plastic surfaces for automobiles are tested with sun creams, sun oils or lotions that, in combination with UV radiation, provide a strong surface load. The test shows that polycarbonate, for example, easily forms stress cracks and degrades prematurely.

  In view of the prior art, it is an object of the present invention to provide a laminate having an excellent property profile comprising at least one thermoplastic substrate and at least one colored layer. The laminate preferably has excellent durability. In particular, it is desirable for the laminate to exhibit chemical resistance that meets very high demands, for example as recently required in the automotive field. Therefore, it is desirable that the laminate particularly has high resistance to cosmetics such as water-in-oil emulsions or oil-in-water emulsions such as sun creams.

  Furthermore, it is desirable that the laminate has stability against mechanical load, and has high weather resistance, high retention, and particularly high UV irradiation resistance.

  Furthermore, it has been a problem to provide a laminate exhibiting high appearance quality particularly against fine streaks, thick streaks, gel bodies and other dirt.

  Furthermore, it is desirable that the laminate can be manufactured with high quality and constant quality at low cost.

  Furthermore, it was an object of the present invention to provide a laminate having a colored layer that can be shaped easily and without substantial loss of quality.

  Furthermore, it is desirable that the printed laminate is provided with a reinforcing layer without the quality of the colored layer being unacceptably impaired.

  However, the above problems as well as the problems not explicitly mentioned which can be easily deduced or inferred from the relevance discussed in the introduction or the following description are solved by a laminate having all the features of claim 1 . Suitable modifications of the laminate are protected in the dependent claims.

  The object of the present invention is accordingly characterized in that at least one thermoplastic substrate comprises polyamide and is provided with at least one colored layer having polyurethane crosslinks on said substrate, A laminate comprising one thermoplastic substrate and at least one colored layer.

  The laminate according to the invention exhibits an excellent property profile. The laminate has excellent durability. In particular, the laminate exhibits chemical resistance that meets high demands such as those recently required in the automotive field. In addition, the laminate has a surprisingly high resistance to water-in-oil or oil-in-water emulsions such as cosmetics, for example sunscreens.

  Furthermore, the laminate is stable against a mechanical load and has high weather resistance, high retention, and particularly high UV irradiation resistance.

  Furthermore, the laminates according to the invention exhibit a high appearance quality, especially with respect to fine streaks, thick streaks, gel bodies and other dirt.

  Furthermore, the laminate of the present invention can be manufactured at a low cost with a high quality and a constant quality.

  Furthermore, the laminate according to the invention with a colored layer can be shaped easily and without any substantial loss of quality.

  Furthermore, the printed laminate can be provided with a reinforcing layer without the quality of the colored layer being unacceptably impaired.

  The present invention provides a laminate. The concept of a laminate essentially represents a feature whose thickness is much less than stretch in length or width. Accordingly, sheets and thin molded bodies are included in the concept.

  The laminate includes at least one thermoplastic substrate and at least one colored layer. The thermoplastic substrate includes polyamide.

  The polyamide in the scope of the present invention is a thermoplastic polymer in which repeating units are bonded with an amide group (—CO—NH—). Polyamides made from essentially aromatic, aliphatic or cycloaliphatic dicarboxylic acids and cycloaliphatic diamines exhibit surprising advantages. Apart from that, it may be an AB type polyamide which can be produced from an aminocarboxylic acid. However, AA / BB type polyamides composed of dicarboxylic acids and diamines are preferably usable. In particular, the polyamide may be PA PACM12 or PA MACM12. In addition, PA11 or PA12 may be used, with reference to conventional nomenclature.

  The polyamides which can be used according to the invention and the substrates produced therewith, in particular polyamide moldings or polyamide sheets, are essentially aromatic, alicyclic or aliphatic dicarboxylic acids, preferably aromatic or preferably by polycondensation. Manufactured from aliphatic dicarboxylic acids and cycloaliphatic diamines. In essence, additional components such as aminoundecanoic acid, monofunctional constituents or further dicarboxylic acids and / or diamines are incorporated up to 40% by weight, preferably up to 10% by weight, particularly preferably incorporated. It means that it is not possible. Alternatively, it may be an AB type polyamide that can be produced from an aminocarboxylic acid. However, AA / BB type polyamides that can be produced from dicarboxylic acids and diamines are preferred.

The alicyclic or aliphatic dicarboxylic acid used is an alicyclic, partially cycloaliphatic, linear or branched dicarboxylic acid having 4 to 20, preferably 8 to 16 carbon atoms. It is. Particular preference is given to dicarboxylic acids having 12 carbon atoms, particularly preferably dodecanedioic acid (formula 1):

  The aromatic dicarboxylic acid used is a dicarboxylic acid having one or more aromatic rings. For example, phthalic acid, isophthalic acid or terephthalic acid.

An alicyclic diamine is an aliphatic diamine having 1 to 3 aliphatic rings consisting of 5 to 8, preferably 6 carbons. Diaminodicyclohexylmethane (formula 2) or 3,3-dimethyl-p-diaminocyclohexylmethane (formula 3) is preferred:

  According to a preferred embodiment, the end group is essentially made from one aliphatic or cycloaliphatic dicarboxylic acid and one cycloaliphatic diamine and is less than 170 mmol / kg, preferably less than 100 mmol / kg. Polyamides having the following ratio may be used: Particularly preferably, the proportion of carboxyl end groups and / or the proportion of amino end groups, preferably the proportion of amino end groups, is less than 100 mmol / kg, particularly preferably less than 35 mmol / kg.

  In a special embodiment, the polyamide contained in the substrate is preferably PA PACM12 or PA MACM12. The polyamide can be obtained from Evonik Degussa GmbH under the trade name TROGAMID®, especially in the form of a molding material, one of the polyamides being TROGAMID® CX7323.

  In another preferred embodiment, it is an aromatic dicarboxylic acid based polyamide.

  Besides polyamides, the substrate may contain further additives, processing aids for sheet production or further plastics. This includes inter alia stabilizers, plasticizers, fillers such as fibers and dyes. However, the proportion of polyamide in the substrate is generally not limited, but is at least 50% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight.

  Since the base material having polyamide is a molded body having a thickness much less than the spread in length or width, like the laminate, the base material containing polyamide is generally an extruded semi-finished product. Accordingly, the substrate is not implying flexibility but may preferably be present in the form of a sheet.

  The substrate which can be provided with a colored layer is preferably used in a thickness of 25 to 5000 μm, in particular 50 to 2000 μm, particularly preferably 100 to 1000 μm. The side to be coated for the substrate as well as the back side thereof may be smooth or have a surface structure, preferably a non-glossy surface on the side that can be coated. For aesthetic reasons, a smooth surface on the uncoated side of the substrate may be preferred.

  Molded bodies or sheets containing the polyamide used as a substrate can be modified during the extrusion process separately to become untreated, transparent and clear sheets or corresponding shaped bodies. Therefore, the sheet or molded body can be colored by adding a colorant such as a pigment and / or a dye. Furthermore, the addition of suitable additives can improve or be affected by scratch resistance, IR or UV absorption or texture. Light scattering can be changed by adding fine particles. Scratch resistance, antifouling action, antifouling or altered texture can also be brought about by corresponding coatings. Hereinafter, the expression “polyamide molded body” may be a synonym for a polyamide sheet.

  In addition to the substrate, the laminate according to the invention comprises at least one colored layer having polyurethane crosslinks. Accordingly, the colored layer comprises a binder that can be cross-linked via an isocyanate.

  The coating used for the production of the colored layer is, for example, rubber elastic in the dry / cured state, and thus can be deformed together with the sheet without deformation during cracking or loss of appearance properties. It may be ink. Thus, as a binder, the paint may preferably comprise cellulose or a cellulose derivative such as nitrocellulose, polyurethane, polyester, polycarbonate, polyamide or poly (meth) acrylate. These polymers can be used alone or as a mixture.

  Preferably, the binder used in the paint may have a weight average molecular weight in the range of 1000 to 50000 g / mol, particularly preferably in the range of 2000 to 20000 g / mol. The number average molecular weight of the binder used is preferably in the range of 1000 to 50000 g / mol, particularly preferably in the range of 2000 to 20000 g / mol. The number average molecular weight and weight average molecular weight can be measured by known methods such as gel permeation chromatography (GPC), preferably using PMMA standards.

  The functional groups essential for the curing of the binder contained in the paint are achieved through hydroxy groups that can be crosslinked with isocyanates or isocyanate derivatives to form polyurethanes. The surprising advantage is achieved in particular by binders having a hydroxyl number in the range from 0.1 to 50 mg KOH / g, particularly preferably in the range from 0.5 to 30 mg KOH / g before crosslinking. The hydroxyl value can be measured, for example, according to DIN EN ISO 4629.

  In addition to the binder having polyurethane crosslinking, the colored layer comprises at least one dye. Dye is a generic name for all substances that give color according to DIN 55943. Substances that impart color include soluble dyes and inorganic or organic pigments, among others. The said pigment | dye can be used individually or in mixture of 2 or more types. And in particular, mixtures of organic color pigments can be used together with soluble organic dyes. In addition, mixtures containing inorganic and organic color pigments can be used. Furthermore, mixtures containing soluble organic dyes in addition to inorganic color pigments can be used. Furthermore, mixtures comprising soluble dyes and inorganic and organic pigments are preferred. The dyes are described, inter alia, in Kirk, Othmer Encyclopedia of Chemical Technology, 3rd edition, volume 19, pages 1-78, and Ullmann's Encyclopedia of Industrial Chemistry-CD5 edition.

  The type of the pigment depends on the processing of the laminate and may require high temperature stability. Accordingly, it is possible to use a pigment that is preferably very temperature stable, so that the pigment does not decompose or sublimate during in-molding or change its color tone depending on the temperature that may occur during processing. I won't let you.

  The pigment preferably contained in the colored layer may be any pigment. For example, but not limited to, titanium dioxide, zinc sulfide, carbon black, azodiaryl yellow, isoindoline yellow, diarylide orange, quinacridone magenta, diketopyrrole red, copper phthalocyanine blue, copper phthalocyanine green, dioxazine violet And diketo metal oxides can be used.

  A very extensive list of additional usable pigments is described in Color Index International, Online 4th Edition, 2001, published by American Association of Textiles Chemists and Colorists by Society of Dyers and Colorists.

  Effect pigments such as, but not limited to, metal oxide coated mica and metallic pigments may also be used. The amount of the colored pigment is usually 1 to 50% by weight, preferably 3 to 45% by weight, based on the weight of the printing ink, depending on the type of pigment, the desired covering power and the printing method selected.

  The white pigment is usually used in an amount of 20 to 50% by mass, preferably 25 to 45% by mass. Colored pigments are often used in amounts of 1 to 20% by weight, depending on the color tone and the type of printing method used. Metal oxide coated mica and metallic pigments are often used in amounts of 1-20% by weight, depending on the color tone and the type of printing method used.

  According to a preferred embodiment of the present invention, the colored layer may be provided with an adhesion promoter layer. The adhesion promoter layer is generally adapted to a binder used in the colored layer and a reinforcing layer that can be provided on the adhesion promoter layer. Preferably, the adhesion promoter layer comprises cellulose or a cellulose derivative such as nitrocellulose, polyurethane, polyester, polycarbonate, polyamide or poly (meth) acrylate. The polymers may be used alone or as a mixture.

  According to a preferred embodiment, the laminate according to the invention may have a reinforcing layer, the colored layer being provided between the thermoplastic substrate and the reinforcing layer. Molding materials and / or sheets that can be used for the production of the reinforcing layer may comprise in particular thermoplastic polymers. Preferred plastics include, among others, cellulose or cellulose derivatives, polystyrene, polystyrene copolymers such as ABS, polyurethane, polyester, polycarbonate, polyamide, polyolefin, especially polyethylene or polypropylene, polyvinyl chloride, poly (N-methylmethacrylamide) (PMMI) and And / or polymethyl methacrylate (PMMA) and the like. The polymers may be used alone or as a mixture. Furthermore, the reinforcing layer may have a filler, in particular fibers.

  The substrate which can be used for the production of the laminate according to the invention can be obtained preferably by an extrusion process, in particular for the production of semi-finished products, which also includes a sheet extrusion process.

  Preferably, an extruder with a single temperature adjustable die, for example as shown in FIG. 1, may be used, said extruder having a die lip (2) and a lip gap (3). Includes a body (1). The die lip (2) is provided with one temperature controller (4).

  According to a special embodiment of the extrusion process, at least the range of the sheet extrusion die, preferably the die lip (2), is 10 ° C. to 100 ° C., preferably 20 ° C. to 80 ° C., particularly preferred than the die body (1). May have a temperature of 30 ° C. to 70 ° C. higher. The temperature of the die lip (2) from 10 ° C to 100 ° C is preferably 20 ° C to 80 ° C, particularly preferably 30 ° C to 70 ° C higher than the temperature of the die body (1), and the die body (1) has a maximum of 5 It is particularly preferred to have a temperature higher by 0 ° C., preferably the same temperature as the extruder.

  According to a special variant of the method, the die body (1) may generally have a temperature between 250 ° C. and 330 ° C. The die lip (2) may have a temperature of 290 ° C. to 370 ° C. at the same time. Preferably, the die lip (2) may have one additional temperature controller (4). The temperature control can be realized through, for example, an inserted heat cartridge or a flat radiator. They can be heated, inter alia, electrically or with a temperature-controlled medium such as oil. The temperature can be measured, for example, with a thermocouple, resistance thermometer, or non-contact temperature measurement method, such as an IR thermometer.

  The indicated temperature is measured as close as possible to the inner wall or inner wall of the extrusion cylinder, as close as possible to the inner wall of the die body or the inner wall of the die body, and as close as possible to the inner wall of the die lip or the inner wall of the die lip. Is done.

  In the inner area of the extrusion tool or the sheet extrusion die before the die exit, volatile components still dissolved in the polymer, for example water or possibly monomers, remain completely in solution, thereby preventing the formation of bubbles Therefore, the melt pressure must be high enough. This can be ensured by, for example, the shape of the extrusion tool, the content of the molding material used in the residual moisture, the volume flow rate of the melt and the processing temperature.

In particular, a preferred method for the production of the substrate can be carried out by the following method steps.
The molding material can be melted in an extruder at a temperature of 250 ° C. to 330 ° C.
• The molding material can exit the extruder through a die lip (2) having a temperature of 290-370 ° C.
The molding material can be drawn over at least one roll or at least one coil with a thickness of 10 μm to 10 mm.
-The molding material can be fed further and cooled.

  As the extruder, any single, twin or multi-screw extruder suitable for processing polyamides may be used. The extruder may or may not have a degassing port, and preferably does not have a degassing port. The extruder may have multiple temperature zones or uniform temperatures in the range of the extrusion cylinder.

  More preferably, the polyamide molding material has a maximum water content of 0.1% by weight, preferably 0.02% by weight. The low water content improves the appearance quality, especially with respect to bubble formation and / or turbidity to be avoided.

  After leaving the extruder, the molding material is cooled. The cooling method is usually adapted to the requirements of the laminate.

Thin laminates, for example sheets having a thickness of up to 250 μm, preferably up to 100 μm, can be produced inter alia by the chill roll method, so that the strip melt is placed on a cooling roll so that the back side of the sheet is at this moment There is no contact with the roll, that is, there is no opposing roll or there is a gloss nip
For example, but not limited to a relatively thick laminate, which can have a thickness of at least 50 μm, preferably at least 100 μm, a glossy method is particularly preferred. The polishing process enables a particularly good surface quality, which is determined by a particularly good thickness distribution of the sheet over the extrusion width, and also the good quality of the roll surface.

  In the polishing method, a plasticized plastic material coming out of a die, preferably a slot die, is guided to a polishing machine, the polishing machine includes a rotating roll connected back and forth, and the plastic material is placed along the rotating roll. At least two rolls are fed so that the nip can be adjusted between a pair of adjacent rolls, and the nip can be used to affect the thickness of the plastic material. In particular, to produce a sheet with a particularly good thickness distribution across the extrusion width, a melt pool / bulge occurs at the first nip directly connected to the melt outlet from the die, thereby causing very fines in the sheet. The setting of the extrusion conditions is selected so that the difference in thickness is made uniform depending on the location. Very generally, the number, arrangement and position of rolls and the number of adjacent pairs of rolls that can set the nip giving the shape can be varied but not limited. And, in particular, I type, F type, L type and Z type arrangements of rolls of polishing machines are known, and all rolls are arranged in a straight line in the I type arrangement. In another arrangement, at least one roll is placed outside one line.

  Preferably, a polisher with at least three rolls A, B and C may be used, and the melt is first fed to the nip 1 between rolls A and B, so that the melt pool D is Are formed in the nip 1 as exemplarily shown in FIG. The roll arrangement of the polishing machine in FIG. 2 corresponds to the I-type arrangement in the horizontal position in this case. A polishing section (E) is subsequently connected to a polishing machine including three rolls A, B and C, which can take up residual heat from the sheet.

  Prior to providing a paint, which can also be referred to as printing ink, the substrate, for example a sheet, may optionally be pretreated. Common pretreatments include cleaning with solvents or aqueous cleaners, flame treatment, UV irradiation, corona treatment, activation using plasma treatment, or ionized gas, such as ionized air, to reduce dust ingress Including processing by.

  The laminate according to the invention comprises a colored layer that can be obtained by providing a paint. In addition to the components, in particular colorants and binders, the paint comprises at least one curing agent or a crosslinking agent that can lead to polyurethane crosslinking.

  Preferred crosslinking agents include in particular polyisocyanates or compounds that liberate polyisocyanates. A polyisocyanate is a compound having at least two isocyanate groups.

  The polyisocyanates which can be used according to the invention may comprise any aromatic, aliphatic and / or alicyclic polyisocyanate.

  Preferred aromatic polyisocyanates include 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, toluidine diisocyanate, 2,6-toluylene diisocyanate, 2,4-toluylene diisocyanate ( 2,4-TDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI), 4,4′-diphenylmethane diisocyanate, monomeric diphenylmethane diisocyanate (MDI) and oligomeric diphenylmethane diisocyanate (polymer MDI) Xylylene diisocyanate, tetramethylxylylene diisocyanate and triisocyanate toluene.

Preferred aliphatic polyisocyanates have 3 to 16 carbon atoms, preferably 4 to 12 carbon atoms in a linear or branched alkylene group, and are suitable alicyclic or (cyclo) aliphatic. The diisocyanate preferably has 4 to 18 carbon atoms, preferably 6 to 15 carbon atoms in the cycloalkylene group. (Cyclic) aliphatic diisocyanates are well understood by those skilled in the art as NCO groups simultaneously attached to the cyclic and aliphatic, for example, as is the case with isofurone diisocyanates. In contrast, an alicyclic diisocyanate is interpreted as having only an NCO group bonded directly to the alicyclic ring, for example H ₁₂ MDI. For example, cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclo-hexane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, heptane diisocyanate, octane diisocyanate, nonane diisocyanate, nonane triisocyanate, for example 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), decane diisocyanate and triisocyanate, undecane diisocyanate and undecane triisocyanate, dodecane diisocyanate and dodecane triisocyanate.

Preferably, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (H ₁₂ MDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4 -Trimethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NBDI). Particularly preferably, IPDI, HDI, TMDI and H ₁₂ MDI are used, and isocyanurates can also be used. In some cases, 4-methyl-cyclohexane-1,3-diisocyanate, 2-butyl-2-ethylpentamethylene-diisocyanate, 3 (4) -isocyanatomethyl-1-methylcyclohexyl-isocyanate, 2-isocyanatopropylcyclohexyl isocyanate 2,4′-methylenebis (cyclohexyl) diisocyanate and 1,4-diisocyanato-4-methylpentane are preferred.

  Preferred aliphatic, cycloaliphatic and araliphatic, ie aryl-substituted aliphatic diisocyanates are described, for example, in Houben-Weyl, Methoden der organischen Chemie, Vol. 14/2, pages 61-70, and W.W. A paper by Siefken, Justie Liebigs Analder der Chemie 562, pages 75-136.

  Of course, mixtures of polyisocyanates may also be used.

Furthermore, oligoisocyanates or polyisocyanates are preferably used, which are derived from said diisocyanates or polyisocyanates or mixtures thereof from urethane structures, allophanate structures, urea structures, biuret structures, uretidione structures, amide structures, isocyanurate structures, carbodiimide structures. , A uretonimine structure, an oxadiazinetrione structure, or an iminooxadiazinedione structure. These preferred classes of polyisocyanates can be produced by dimerization, trimerization, allophanatization, biuretization and / or urethanization with simple diisocyanates. Such compounds having more than two isocyanate groups per molecule include, for example, simple diisocyanates such as IPDI, TMDI, HDI with polyhydric alcohols (eg glycerin, trimethylolpropane, pentaerythritol) or polyvalent polyamines. And / or reaction products of triisocyanurate obtained by trimerization with H ₁₂ MDI, or simple diisocyanates such as IPDI, HDI and H ₁₂ MDI, with HDI biurets being particularly preferred.

  Of particular interest are paints which comprise preferably 0.5 to 20% by weight, particularly preferably 2 to 10% by weight, of crosslinking agent, based on the total weight of the paint.

  When a polyisocyanate is used as a crosslinking agent, the reaction of the hydroxy group contained in the binder with the organic polyisocyanate is 0.5 to 1.1 per hydroxy group depending on the intended use of the reaction product. The NCO group of In the reaction, the amount of organic polyisocyanate is preferably present in an amount of 0.7 to 1.0 isocyanate groups per hydroxy group relative to the total hydroxy content of the components present in the reaction mixture. To be implemented.

  The paint may contain further common solvents, additives and / or processing aids, said components usually being adapted to the printing technology and application requirements.

  And general solvents, additives and / or processing aids are described in detail in EP06888839B1, said solvents, additives, processing aids etc. being inserted into the present application for the purpose of disclosure.

  Further properties of the paint depend on the printing method, and these properties are detailed in Kipphan, Handbuch der Printmedia, Springer-Verlag, Berlin, 2000, ISBN-103540669418, which are described in this application for the purpose of disclosure. Has been inserted.

  A particularly suitable printing ink is obtained, for example, under the name NoriAmid® from Proell KG, Weissenburg, Bavaria, Germany.

  The paint can be provided on the substrate by a known method, preferably a printing method. Suitable printing methods for providing the printing ink layer are known and in principle any printing method, for example letterpress printing, intaglio printing, flexographic printing, offset printing, screen printing, pad printing, digital printing, in particular inkjet printing and Laser printing is preferred. Intaglio printing, flexographic printing and screen printing are preferred, and screen printing is particularly preferred. Regarding the screen printing method, flat bed screen printing is preferred. Said printing method is described inter alia in Kipphan, Handbuch der Printmedia, Springer-Verlag, Berlin, 2000, ISBN-103540669418, which is inserted into this application for the purpose of disclosure.

  Following printing, the coating is cured by conventional methods and dried upon use of the solvent. Curing time or drying time can vary depending on the type and amount of solvent and the degree of crosslinking. Preferably, the curing time or drying time is selected to maintain sufficient elasticity for the shaping process in which the colored layer can occur, but the colored layer has sufficient strength for possible shaping and further processing. It is strongly cross-linked to have. A drying time or curing time of at least 5 minutes, particularly preferably at least 10 minutes, and particularly preferably at least 20 minutes at a temperature of about 50 ° C., or 90 ° C. depending on the dryer, is often sufficiently high for the colored layer to be stable Bring sex. For the above reasons, if the drying time is too long, the brittleness of the colored layer that makes shaping difficult may appear, so it is desirable that the drying time is not too long. In this case, curing is temperature dependent. Thus, a surprising advantage is achieved at 50 ° C. when the drying time is at most 20 hours, preferably at most 10 hours. The relatively high temperature accelerates the drying process, so that at 90 ° C., the drying time is preferably at most 5 hours, preferably at most 4 hours.

  When an adhesion promoter layer is provided on a substrate provided with a paint, the adhesion promoter layer may be dried together with the paint, and the curing of the paint is performed during the drying of the adhesive layer. Good. The adhesion promoter layer may be provided on the substrate by the same method as the colored layer, and the colored layer and the adhesion promoter layer are particularly preferably printed by a screen printing method, particularly flat bed screen printing.

  Printed laminates produced according to the invention, preferably polyamide seals, particularly preferably flexible polyamide sheets, are used inter alia for molding materials, wood, glass or metal, preferably for molding materials can do.

  Lamination can be performed, for example, by attaching to the surface of the laminate, and the lamination can be performed on the printed or non-printed side. Furthermore, hot lamination of the sheet to another sheet or plate is also possible. The sheet according to the invention can be laminated with one or more carrier sheets.

A substrate provided with a crosslinked colored layer can be shaped by known methods, the type of shaping method and the process parameters being determined by the application purpose and properties of the laminate. Surprisingly, the laminate according to the invention can be molded by deep drawing, thermoforming or high pressure deformation.
As a basis, for example, when the sheet thickness is 250 μm and the deformation depth is 1.2 mm, the following parameters can be set.

  Upper and lower heating limits: 270 to 300 ° C, preferably 280 to 290 ° C.

  Heating time 5-15 seconds, preferably 8-10 seconds.

  Air heating 280-340, preferably 300-320 ° C.

  Tool heating 90-130 ° C, preferably 100-110 ° C.

  High pressure about 100-200 bar, preferably 140-160 bar.

  High pressure time is about 2-8 seconds, preferably about 3-5 seconds.

  In addition, a polyamide sheet having one or more polymer materials, such as molding materials, may be in-mold. This may be done especially after shaping. In another method, the molded body obtained from the molding material and optionally a laminate that can be shaped can of course be bonded together.

  The optionally shaped laminate may be in-molded by a normal injection molding method. Commonly used injection molding materials that may be used to in-mold laminates that include crosslinked colored layers together include, but are not limited to, polyamides, polyesters, polycarbonates, polystyrenes, polystyrene-copolymers, such as ABS, poly (N-methylmethacrylamide) (PMMI) and / or polymethylmethacrylate (PMMA). A preferred material for in-molding is polyamide or polymethyl methacrylate.

  Furthermore, the laminate may be subjected to one or more of the following processing steps before or after providing the reinforcing layer. That is, the sheet is shaped with or without heating and trimmed. The processing of the sheet is not limited to the above method. These processing methods may be performed in a different order from the above method. Similarly, the processing step may be repeated one or more times.

  In the following, the present invention will be described in detail based on examples, although not limited thereto.

Schematic of temperature adjustable die. Schematic of roll arrangement.

Production Example Production of Polyamide Sheet The water content was measured according to Karl Fischer titration. The end group measurement is performed using titration.

Manufacture of a polyamide sheet or a polyamide molded body A polyamide sheet was manufactured by a method known per se, for example, by a slot die in the case of flat sheet extrusion, inflation extrusion molding, or by a solution casting method.

  Plastic moldings can also be carried out in multiple layers, optionally by extrusion coating adhesion or subsequent laminating.

  The said manufacture example was manufactured with the commercial flat sheet extruder made from Collin. Here, the polyamide is preferably in the form of granules, placed in a hopper, and sent to the extruder by the hopper. The extruder is composed of a metal cylinder and an extrusion screw heated from the outside, and the extrusion screw rotates in the extruder, whereby the polymer is fed from the suction port inside the hopper opening by the extruder. In other embodiments, a twin screw extruder or a multi-screw extruder can also be used. The polymer melted by external heating and shearing of the polymer in the extruder and reached the extrusion tool in the form of a sheet extrusion die (or generally a slot die) on the back side of the extrusion screw tip. Here, the polyamide melt is sent in a flat state and exits the sheet extrusion die in a flat state through a die nip. The sheet extrusion die can feed the melt from a plurality of extruders, thereby creating a multilayer sheet. Subsequently, the strip of plastic was cooled on at least one roll and then wound up.

  The extruder used for the experiment, which is connected to the cylinder, has two separately temperature-controllable extrusion zones and is not equipped with a degassing port, has an L / D ratio (screw length / screw The diameter of the screw was 25 mm and 35 mm. A commercially available three-zone screw was used.

For the experiment, the following temperature settings were made with an extruder.
Inhalation (area inside the hopper): 240 ° C
Extrusion zone 1: 280 ° C
Extrusion zone 2: 290 ° C
Transition range: 290 ° C
Sheet extrusion die: 290 ° C
Lip temperature controller: 350 ° C.

Another form of the method, the A-chill roll method sheet, is produced in a single layer by a so-called chill roll method in an experimental apparatus, and has a thickness of 50 μm. The sheet was then visually evaluated for quality. To that end, the sheets were compared and evaluated in comparison with a reference sample that was in marketable quality with respect to appearance quality. Appearance quality is understood here as inter alia the size of the streaks, the surface quality, the number of gel bodies, the number of soils and the number of particles from degraded material. Here, all the samples judged to be sellable were evaluated (+). Samples that were not available for sale were rated (○), and samples that were clearly or very not sold were rated (-) or (-).

  Polyamide PA1 is, for example, polyamide PA PACM 12 manufactured by Evonik Degussa GmbH based on the composition of TROGAMID® CX7323. Polyamide PA2 is a medium viscosity PA PACM 12.

Process variant B-Glossing process The plastic melt obtained by the extrusion process is divided into two adjacent rolls (A + B) with a nip set at 250 μm, as well as a roll (C) connected earlier. Shaped and cooled. The arrangement of the rolls is explained in more detail in FIG. In order to produce a particularly good thickness distribution, here a small shape of the melt nip (D) is present which is small in shape over the extrusion width. The roll arrangement of the polishing machine corresponds in this case to an I-shaped arrangement in a horizontal position, and another polishing machine may be used for the production of the sheet. A cooling section (E) is continuously connected to the polishing machine consisting of three rolls A, B and C, which removes residual heat from the sheet.
Roll A temperature: 70 ° C
Roll B temperature: 80 ° C
Roll C temperature: 140 ° C.

  A 250 μm sheet having a particularly excellent appearance quality and a particularly excellent thickness distribution was obtained.

EXAMPLE A 250 μm thick sheet of TROGAMID® CX7323 obtained by polishing according to the method in variant B of the above method was prepared for the subsequent shaping step using a laser (centering pin Accommodation hole). On the prepared sheet, a commercially available printing ink made by Proell KG, which allows isocyanate crosslinking, was printed by screen printing (NoriAmid®). The printing ink was mixed with an isocyanate curing agent (curing agent 8125, obtained from Proell KG) and a diluent (SMK090, obtained from Proell KG) was added to adapt the viscosity to the viscosity requirements. Subsequently, an adhesion promoter layer (NoriAmid® APM, obtained from Proell KG) was provided.

Here, the decoration / layout was implemented as follows.
Letter color (logo): NoriAmid® 770 + 10% curing agent 8125 + 10% SMK090
Background color: NoriAmid® 952 + 10% curing agent 8125 + 10% SMK090
Adhesion promoter: NoriAmid® APM + 10% SMK090.

Print parameter printing was performed on 100-40y fabrics without pre-temperature control.
All layers were dried in a jet dryer immediately following printing. Here, each zone was set to the following temperature: 85 ° C / 90 ° C / 25 ° C. The coil speed was 5 m / min.
Subsequently, quenching of the printed sheet (including the adhesion promoter layer) is performed at 90 ° C. for 3 hours.

  The printed sheet is printed on the Niebling-Junior Kunststofferberitung-Werckzeugbau e. The cover was molded by a molding machine SAMK400-42 commercially available from K company.

Process parameters-suffix:
High pressure (setting / actual) 150bar / 145bar
High pressure time Total: 4 seconds (150 bar, rise time: 1 second)
Heating time: 8 seconds Heating upper / lower limit: 280 ° C
Air heating: 300 ° C
Tool heating: 110 ° C.

  From the above setting, a sheet temperature (back surface) of about 120 to 125 ° C. was generated. The cycle time was 21.1 seconds.

  After punching out the cover of the seat box, in-mold molding of the seat insert by TROGRAMID (registered trademark) CX7323 is performed in accordance with Makrolon (registered trademark) 2205.

Process parameters-In-mold molding process cylinder temperature for TROGAMID® CX7323: 310/300/290/280 ° C
Injection time: 0.6 seconds Injection pressure: 1200 bar
Re-pressurization: 500 bar
Repressurization time: 5 seconds Cooling time: 15 seconds Tool temperature: Die side: 75 ° C, ejection side: 35 ° C.

Process parameters—In-mold process cylinder temperature for Makrolon® 2205: 290/280/275/265 ° C.
Injection time: 0.6 seconds Injection pressure: 1500 bar
Repressurization: 570 bar
Repressurization time: 4 seconds Cooling time: 15 seconds Tool temperature: Die side: 75 ° C, ejection side: 35 ° C.

  A laminate having an outstanding property profile that satisfies high aesthetic requirements and also exhibits excellent resistance to chemical and mechanical loads was obtained.

Claims (15)

  At least one thermoplastic substrate comprising at least one thermoplastic substrate, the substrate being provided with at least one colored layer having polyurethane crosslinks, and at least A laminate comprising one type of colored layer.   The laminate according to claim 1, wherein the laminate has an adhesion promoter layer provided on the colored layer.   The laminate according to claim 1, wherein the laminate has a reinforcing layer, and the colored layer is provided between the thermoplastic base material and the reinforcing layer.   The laminate according to any one of claims 1 to 3, wherein the thermoplastic substrate has a thickness in the range of 25 µm to 5000 µm.   5. A flat thermoplastic substrate provided with a colored layer, wherein the binder present in the paint is cross-linked with a polyisocyanate. A method for producing a laminate.   6. The method according to claim 5, characterized in that the binder has a weight average molecular weight in the range of 1000 to 50000 g / mol.   7. A method according to any one of claims 5 or 6, characterized in that the binder has a hydroxyl value in the range of 0.1-50 mg KOH / g.   8. A method according to any one of claims 5 to 7, characterized in that the binder comprises cellulose or cellulose derivatives, polyurethane, polyester, polycarbonate, polyamide or poly (meth) acrylate.   9. Process according to any one of claims 5 to 8, characterized in that an aliphatic polyisocyanate is used for the crosslinking.   10. A method according to any one of claims 5 to 9, characterized in that the paint is printed on a polyamide sheet using a screen printing method.   11. The method according to claim 5, wherein an adhesion promoter layer is provided on the colored layer obtained by printing with a paint.   12. A method according to claim 11, characterized in that the adhesion promoter comprises cellulose or cellulose derivatives, polyurethane, polyester, polycarbonate, polyamide or poly (meth) acrylate.   13. A method according to any one of claims 11 or 12, characterized in that the adhesion promoter is printed on the colored layer using a screen printing method.   14. A method according to any one of claims 5 to 13, characterized in that the printed polyamide sheet is shaped.   15. A method according to any one of claims 5 to 14, characterized in that the printed polyamide sheet is provided with a reinforcing layer.

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